Complex coacervation is known as liquid-liquid phase separation in aqueous solution by spontaneous aggregation associated with electrostatic matching between two oppositely charged polyelectrolytes. Complex coacervates have been used for direct complexation between bioactive molecules and polysaccharides, micro- or nanoencapsulation of bioactive molecules or cells, and surface coating of particles, due to their unique physicochemical characteristics that can be easily modulated by pH, ionic strength, charge density, and stoichiometry of interacting molecules. However, these systems often require cytotoxic surfactants and/or expensive equipment. The ability to cheaply form cytocompatible coacervates under mild conditions that permit the compartmentalized encapsulation of cells and bioactive factors via simple mixing would be valuable for tissue engineering strategies as it would allow for control over their spatial distribution. However, no coacervate system has been reported capable of simultaneous cell encapsulation and the formation of drug-laden microdroplets under physiological conditions that could be used as a three-dimensional biomaterial for cell encapsulation and transplantation, and tissue engineering applications, due to the harsh physicochemical conditions [i.e., low pH (<4) and high temperature (˜60° C.)] typically required for complex coacervation formation.